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  • self-assembly  (23)
  • catalysis  (20)
  • 1
    ISSN: 0947-6539
    Keywords: adenine ; catalysis ; molecular recognition ; template effects ; transition states ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of receptors were prepared all containing two adenine binding sites linked by various spacers. Their ability to act as templates in the coupling of two adenine derivatives, an active ester and an amine, in CHCl3 was evaluated. The accelerations varied from none to 700-fold. Binding studies of the coupling product with these templates confirmed involvement of both binding sites. When the spacer was a 1,10-phenanthroline unit, an efficient hydrolysis reaction of the active ester was observed. Another series of receptors were prepared containing one adenine receptor and various polar functional groups. The molecules were evaluated as catalysts in the coupling of an adenine-derived active ester and n-butyl-amine. The orientation as well as the nature of the functional group greatly influenced the coupling rate. A carboxylate group was most effective, accelerating the intracomplex reaction 250-fold.
    Additional Material: 7 Ill.
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  • 2
    ISSN: 0947-6539
    Keywords: benzyl ligands ; catalysis ; chromium compounds ; ferromagnetic coupling ; polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of [{Cp*Cr(μ-Cl)}2] with benzyllithium yielded [{Cp*Cr-(μ-Bz)}2] (1), a CrII alkyl complex with bridging benzyl groups and a Cr—Cr bond, which rearranged at room temperature to [Cp*Cr(η1-Bz)(μ-η3:η6-Bz)CrCp*] (2), a mixed valent (CrI/CrIII) complex with a benzyl ligand coordinating as an η6-arene ligand to one chromium and as an η3-allyl ligand to the other one. Upon heating, 2 reductively eliminated bibenzyl and yielded [(Cp*Cr)2(μ-η6:η6-Bz-Bz)] (3), in which two 17-electron sandwich complexes are linked by an ethano bridge. The crystal structures of 2 and 3 have been determined. Magnetic susceptibility and saturation magnetization measurements showed 2 to be ferromagnetically coupled (ground state S = 2, J = + 23(1) cm-1). Of the three isomers, only 2 catalyzed the polymerization of ethylene, presumably because it contains a CrIII alkyl.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0947-6539
    Keywords: allylhydrazines ; cadmium compounds ; catalysis ; photochemistry ; zinc compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Suspensions of zinc or cadmium sulfide powders in a protic solvent catalyse the linear addition of enol ethers and olefins to 1,2-diaryl- and 1-aryl-2-alkyl-1,2-diazenes, producing allylhydrazine derivatives. Relative quantum yields decrease sharply when the 1,2-diazene is more difficult to reduce, while their relationship to the oxidation potential of the enol ether/olefin is complicated. Reduction to 1,2-diarylhydrazine and concomitant dehydrodimerization of the enol ether occurs as a side reaction. It is favoured by increasing light intensity and becomes the major reaction path when platinized (5 mol%) photocatalysts are employed. It is proposed that the photogenerated electron-hole pair in a proton-coupled electron transfer reduces the diazene to a hydrazyl radical and oxidizes the olefin/enol ether to a radical cation. The allylic radical obtained from the latter by deprotonation then undergoes C—N coupling with the hydrazyl radical to afford the allylhydrazine. Diarylhydrazine formation occurs by disproportionation of the hydrazyl radical or by a successive proton-coupled reduction. Thus photoaddition can be classified as a 1 e-/1 h+ process while 2e-/2h+ are necessary for the reduction.
    Additional Material: 3 Ill.
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  • 4
    ISSN: 0947-6539
    Keywords: catalysis ; crystal structure ; oxidations ; rhenium peroxo complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rhenium oxides Re2O7 and ReO3 react with hydrogen peroxide solutions yielding peroxo complexes that efficiently catalyze the oxidation of olefins, aromatics, and certain organometallic compounds. In contrast, related oxides of molybdenum (MoO3) and vanadium (V2O5) do not activate H2O2 under comparable conditions. The active rhenium peroxo complex was isolated from the system Re2O7/H2O2: the crystalline red-orange, explosive compound of formula H4Re2O13 is the most oxygen rich rhenium compound isolated to date. Its structure resembles a “peroxo perrhenic acid”. The binuclear compound could be isolated in the form of a diglyme adduct, structurally defined as two corner-sharing pentagonal bipyramids with apical oxo and aquo ligands; the equatorial positions are occupied by the bridging oxygen and by n2-peroxo groups (two [O2]2- ligands per rhenium). In contrast to the known complex [CH3ReO(O2)2].H2O, the new peroxo species [O{ReO(O2)2.H2O}2] decomposes hydrolytically during the catalytic cycle and can thus not compete in terms of catalytic activity in oxidation reactions involving H2O2. Hydrolysis yields “perrhenic acid” Re2O7.2H2O, the diglyme adduct of which compound was also characterized by means of an X-ray diffraction analysis.
    Additional Material: 6 Ill.
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  • 5
    ISSN: 0947-6539
    Keywords: alkylthiols ; gold ; nanoparticles ; phase transitions ; self-assembly ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Self-assembled monolayers (SAMs) of n-alkanethiolates on gold, silver, and copper have been intensively studied both as model organic surfaces and as modulators of metal surface properties. Sensitivity restrictions imposed by monolayer coverage and the low surface area of planar metal substrates, however, limit the characterization of these films in molecular terms to surface enhancement techniques. As a result, key aspects such as film dynamics and alkyl chain ordering remain ill-defined. The characterization of the thermal behaviour of SAMs is important not only for the design of stable, well-ordered organic superlattices, but also for the fundamental understanding of the factors that drive molecular interactions in two dimensions. Phase properties in SAMs have been addressed here through the synthesis of gold nanoparticles of 20-30 Å in diameter and fully covered with alkylthiol chains. These thiolmodified gold nanoparticles with large surface areas have enabled the monolayer film structure to be uniquely characterized by transmission FT-IR spectroscopy, NMR spectroscopy, and differential scanning calorimetry. Our studies reveal that for long-chain thiols (≥ C16), the alkyl chains exist predominantly in an extended, all-trans ordered conformation at 25°C. Furthermore, calorimetry, variable temperature transmission FT-IR spectroscopy, and solid-state 13C NMR studies have established that a cooperative chain melting process occurs in these alkylated metal colloids. How this arises is not immediately evident, given the relation between the extended chain conformation and the geometry of the spherical nanoparticles. Transmission electron microscopy (TEM) reveals that adjacent gold particles are separated by approximately one chain length; this suggests that chain ordering arises from an interdigitation of chains on neighboring particles. The thermotropic behavior is sensitive to the alkyl chain length and chain packing density. The alkylated nanoparticles can thus serve as a highly dispersed analogue to the much-studied planar SAMs.
    Additional Material: 7 Ill.
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  • 6
    ISSN: 0947-6539
    Keywords: bridging ligands ; chelate ligands ; copper complexes ; self-assembly ; structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The “self-assembly” reaction between bischelating 2,2′-bipyrimidine, metallic copper, Cu2+, and two equivalents of bidentate Ph2P(CH2)nPPh2 produces crystallographically characterized dinuclear complexes with a [Cu1(μ-bpym)-Cu1]2+ core and chelating (n = 5; type I) or bridging diphosphine ligands (n = 6, 8; type II). Structures II may be designated as “inverse cryptate” arrangements. The structural data of the solids and the spectroscopic results for the dissolved species indicate a strained configuration in the case of complex [(μ-bpym)Cu2{μ-Ph2P-(CH2)n]2+ (6) with n = 6. Once the polymethylene chain length is reduced one notch further to n = 5 (5), the diphosphines can no longer bridge but help to form eight-membered chelate rings (structure I). In this complex there is a distortion towards a trigonal-pyramidal coordination geometry at the copper(I) centers, which is supported by the formation of an “organic sandwich” arrangement between the central bpym acceptor and two phosphino phenyl rings.
    Additional Material: 5 Ill.
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  • 7
    ISSN: 0947-6539
    Keywords: catalysis ; cobalt ; cofactors ; redox systems ; ruthenium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis as well as the chemical and electrochemical properties of homoleptic and heteroleptic (trispyridyl-methylamine as coligand) transition-metal complexes (Ru and Co) of 1,10-phenanthroline-5,6-dione (PD) and of its N-monomethylated derivative (PDMe+) are described. In particular, their ability to abstract hydride ions was studied. Electrochemical investigations with cyclic voltammetry, rotating disk electrode experiments, and spectroelectrochemical methods at different pH values gave an insight into the complex electrochemistry of the compounds described, which is strongly influenced by a hydration pre-equilibrium. The electrochemically active quinone form of the transition-metal complexes can be reduced to the hydroquinone state in acidic solution and to their transition-metal-stabilized semi-quinone states for neutral and basic solutions, whereas PDMe+ is reduced to the hydroquinone state in both acidic and neutral solutions. The compounds can also be reduced chemically, and are efficient catalysts for the indirect oxidation of the enzymatic cofactor NAD(P)H. For the indirect aerobic NAD(P)H oxidation, up to 900 turnovers per hour can be observed, an achievement yet to be reached by other catalyst systems.
    Additional Material: 9 Ill.
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  • 8
    ISSN: 0947-6539
    Keywords: catalysis ; colloids ; gold-palladium colloids ; HRTEM ; hydrogenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Layered bimetallic gold-palladium colloids in the size range of 20-56 nm have been synthesized by the seed=growth method: gold seeds were convered by palladium layers of various thickness and vice vaers. The outer metal was coordinated by trisulfonated triphenylphosphine and sodium sulfanilate ligands to stabilize the bimetallic particles to such an extent that they could be isolated in the solid state. Owing to the hydrophilic ligand shell, redispersion in water was posible in any concentration. High-resolution transmission electronn microscopy and energy-dispersive X-ray analysis was used to characterized the colloids. Stabilized and nonstabilized gold-palladium and palladium-gold systems on a TiO2 support were used as heterogeneous catalysts for the hydrogenation of hex-2-yne to cis-hex-2-ene. Both the palladium-plated gold seeds and the gold-plated palladium particles showed considerably increased activities compared with the pure metals. The ligand shell seems not to influence the catalytic behavior because protected and unprotected colloids behave very similarly.
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  • 9
    ISSN: 0947-6539
    Keywords: catenanes ; macrocycles ; rotaxanes ; self-assembly ; tetrathiafulvalenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general stepwise approach is described for the preparation of tetrathiafulvalene (TTF)-based linear and monoand dimacrocyclic compounds incorporating one or two 1,4-dioxyphenylene, 9,10-dioxyanthrylene, or 1,5- or 2,6-dioxynaphthylene units from readily available starting materials. By utilizing the π-π stacking interactions of the TTF unit with the dipyridinium dication of 1,1′-[1,4-phenylenebis (methylene)] bis-4,4′-bipyridinium bis(hexafluorophosphate), a rotaxane and two [2]catenanes were synthesized starting from the linear and monomacrocyclic compounds, respectively. From the dioxyphenylene-based dimacrocycle, three [3]pseudocatenanes (trans, cis, and a mixture of cis/trans isomers) were obtained with the trans compound as the major product. From the dioxyanthrylene dimacrocycle, only the trans-[3]pseudocatenane was obtained. Catenane products were formed quantitatively from the 1,5-dioxynaphthylene dimacrocycle in a template-directed reaction, affording a trans-[3]pseudo-catenane together with a [4]pseudocatenane (mixture of cis/trans isomers). From the 2,6-dioxynaphthylene dimacrocycle, a cis-[3]pseudocatenane was obtained as the major product and a trans-[3]pseudocatenane as the minor one. For the [3]pseudocatenanes (i.e., both the cis and trans catenanes), in which the TTF units were clamped by the tetracationic macrocycle, isomerizations were completely prevented even in the presence of trifluoroacetic acid. All new rotaxanes and catenanes were characterized by electrospray mass spectrometry, and the cis- and trans- [3]pseudocatenanes were additionally investigated by 1H NMR spectroscopy. The electrochemical and spectral properties of the rotaxane and the catenanes are reported. Catenane formation increases the redox potentials of the TTF unit. The results demonstrate the versatility of TTF as a building block in the construction of supramolecular structures.
    Additional Material: 4 Ill.
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  • 10
    ISSN: 0947-6539
    Keywords: crown ethers ; dialkylammonium salts ; hydrogen bonding ; molecular recognition ; pseudorotaxanes ; self-assembly ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A very simple self-assembling system, which produces inclusion complexes with pseudorotaxane geometries, is described. The self-assembly of eight pseudorotaxanes with a range of stoichiometries-1:1, 1:2, 2:1, and 2:2 (host:guest)-has been achieved. These pseudorotaxanes self-assemble from readily available components-well-known crown ethers, such as dibenzo[24]crown-8 and bis-p-phenylene[34]crown-10, and secondary dialkylammonium hexafluorophosphate salts, such as (PhCH2)2NH+2PF-6 and (nBu)2NH+2PF-6-and have been characterized not only in the solid state, but also in solution and in the “gas phase”. The pseudorotaxanes are stabilized largely by hydrogen-bonding interactions and, in some instances, by aryl-aryl interactions.
    Additional Material: 40 Ill.
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